大孔树脂支载CBS催化剂的制备及催化性能  

Preparation of Macroporous Resin Supported CBS Catalyst and Its Catalytic Properties

作　　者：戴双雄 李国华[1] 张翠燕 黄迪[1] 宋晓玲 韩佩言 程硕 

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《精细化工》2017年第11期1265-1271,1282,共8页Fine Chemicals

摘　　要：以1,1-二苯基-1-[(2S,4R)-4-(4-乙烯基-苄氧基)-2-吡咯烷基]-甲醇(Ⅱ)为功能性单体,经苯乙烯共聚、二乙烯苯交联后与甲基硼酸进行缩合反应,制备了大孔树脂支载的CBS(手性口恶唑硼烷类化合物)催化剂(Ⅳ),并应用于催化苯乙酮不对称还原反应。利用红外光谱对催化剂Ⅳ进行了表征,并考察了交联度、功能性单体摩尔分数及催化剂的循环使用性能对催化反应的影响。还原产物(R)-1-苯乙醇(Ⅵ)采用红外、核磁共振(1HNMR、13CNMR)进行了结构表征。对催化剂在自建的连续反应装置上的催化性能进行了评价。结果表明:当支载催化剂的交联度为8%,功能性单体摩尔分数为9.67%时,连续催化苯乙酮不对称还原为(R)-1-苯乙醇的转化率接近100%,ee(对映体过量)值接近90%。催化剂连续使用25 h后,ee值没有降低的趋势。A novel macroporous resin supported CBS（chiral xazaborolidine） catalyst（Ⅳ） was prepared by copolymerization between 1,1-diphenyl-1-[（2 S,4 R）-4-（4-vinyl-benzyloxy）-pyrrolidin-2-yl ]-methanol（Ⅱ） and styrene,followed by crosslinking with 1,2-divinylbenzene,then,condensation with methylboronic acid.Catalyst Ⅳ was characterized by means of FTIR,and then applied in the catalytic asymmetric reduction of acetophenone into（R）-1-phenylethanol（Ⅵ）.The effects of degree of crosslinking,mole percent of functional monomer（Ⅱ） and recycling times on the catalytic properties of catalyst were investigated.Compound Ⅵ was confirmed by FTIR and nuclear magnetic resonance（NMR）spectroscopy.Besides,a continuous reaction device for reduction of acetophenone was established to study the catalytic properties of catalyst Ⅳ.The results showed that when the degree of crosslinking of catalyst was 8% and the mole percent of functional monomer Ⅱ was 9.67%,the conversion of acetophenone into（R）-1-phenylethanol approached 100 % and the ee value was about 90% in the continuous reaction.Even after catalyst Ⅳ continuously worked for 25 hours,the ee value was not decreased.

关 键 词：大孔树脂支载 CBS催化剂 不对称还原 连续反应 

分 类 号：O643.38[理学—物理化学] O632.13[理学—化学]